Wang Chao, Wang Shou-Juan, Kong Fan-Gong
Key Laboratory of Pulp and Paper Science & Technology of Ministry of Education, Qilu University of Technology (Shandong Academy of Sciences), No. 3501 University Road, Jinan, 250353, China.
Inorg Chem. 2021 Apr 5;60(7):5034-5041. doi: 10.1021/acs.inorgchem.1c00063. Epub 2021 Mar 8.
Three photosensitive butylcalix[n]arene (TBC[n], n = 4, 6, 8)-protected titanium-oxo clusters (TOCs), formulated as [Ti(μ-O)(TBC[4])(OPr)(DEF)]·DEF (, , DEF = ,-diethylformamide), [Ti(μ-O)TBC6]·HO (, ), and [Ti(μ-O)(OPr)TBC8]·DEF (, ), were successfully synthesized and characterized. Because of the generation of charge transfer from TBC[n] to the TiO core, the three TBC[n]-decorated TOCs show a broadened visible-light absorption and narrowed optical band gap based on the UV-visible spectra and density functional theory calculations. The corresponding photosensitive electrodes prepared using these three TOCs exhibit stable photocurrent responses. Furthermore, their photocatalytic performances for hydrogen evolution and methylene blue degradation were evaluated, and all of the materials display excellent photocatalytic activity and stability. The calixarene-Ti coordination is therefore an effective strategy to enlarge the visible-light absorption band of Ti-O materials and improve their photoelectric/photocatalytic performances.
成功合成并表征了三种由光敏性丁基杯[n]芳烃（TBC[n]，n = 4、6、8）保护的钛氧簇（TOC），其化学式分别为[Ti(μ-O)(TBC[4])(OPr)(DEF)]·DEF（ ， ，DEF = N，N-二乙基甲酰胺）、[Ti(μ-O)TBC6]·H₂O（ ， ）和[Ti(μ-O)(OPr)TBC8]·DEF（ ， ）。基于紫外可见光谱和密度泛函理论计算，由于从TBC[n]到TiO核发生电荷转移，三种TBC[n]修饰的TOC显示出拓宽的可见光吸收和变窄的光学带隙。使用这三种TOC制备的相应光敏电极表现出稳定的光电流响应。此外，评估了它们在析氢和亚甲基蓝降解方面的光催化性能，所有材料均表现出优异的光催化活性和稳定性。因此，杯芳烃 - 钛配位是扩大Ti - O材料可见光吸收带并改善其光电/光催化性能的有效策略。
